Linear aromatic polyesters



United States Patent 3,505,289 LINEAR AROMATIC POLYESTERS Andr Jan Conix, Antwerp, and Urbain Leopold Laridon,

Wilrijk-Antwerp, Belgium, assignors to Gevaert Photo- Producten N.V., Mortsel, Belgium, a Belgian company No Drawing. Continuation of application Ser. No. 62,076,

Oct. 12, 1960, which is a continuation-in-part of application Ser. No. 797,587, Mar. 6, 1959. This application Feb. 24, 1965, Ser. No. 435,079

Claims priority, application Belgium, Mar. 7, 1958,

65,478; Dec. 22, 1959, 585,882 Int. Cl. C08g 17/08, 17/13 US. Cl. 260-49 4 Claims The present invention is concerned with the production of high-molecular weight linear aromatic polyesters, more particularly with the production of high-molecular weight linear aromatic polysulfonates and with a process and catalysts for their preparation.

The present application is a continuation of our application Ser. No. 62,076, filed Oct. 12, 1960, which on its turn is a continuation-in-part of our application Ser. No. 797,587, filed Mar. 6, 1959, both of which are now abandoned.

In U.S.P. 2,035,578 there are described polysulfonates obtained from polysulfonic acids and polyhydric phenols, but it is stated that these resins are not so valuable as those prepared from polycarboxylic acids. They are frequently darker in color, have poorer water resistance and poorer solubilities.

It is an object of the present invention to provide a process for obtaining very high-molecular weight linear aromatic polysulfonates.

A further object of the invention is to procure aromatic polysulfonates with improved solubility properties in organic solvents and having a very high water resistance.

A still further object is to provide catalysts allowing the preparation of polymers having especially highmolecular weights and making it possible to carry out the reaction at room temperature and at atmospheric pressure.

Still further objects will appear from the following description and claims.

According to the present invention, highly polymeric linear aromatic polysulfonates are prepared by condensation of one or more diacid halides of aromatic disulfonic acids, dissolved or dispersed in an organic liquid which is a solvent or a swelling agent for the polysulfonate to be formed and which is immiscible with water, with an aqueous solution of one or more alkali diphenates.

Also according to the invention, highly polymeric linear aromatic polysulfonates are obtained by replacing in the above described polycondensation reaction, the diacid halides of aromatic disulfonic acids by a mixture of one or more diacid halides of aromatic disulfonic acids and one or more diacid halides of dicarboxylic acids.

This mixture may also be in part or wholly replaced by one or more diacid halides of aromatic monocarboxysulfonic acids.

Further, according to the invention, the polycondensation of alkali diphenates with the diacid halide is carried out in the presence as catalysts of one or more oni'um compounds such as quaternary ammonium compounds. These catalysts are preferably added in amounts between 0.01 and 5%, calculated on the weight of the diphenate or diphenates used. The most effective catalysts are soluble in the aqueous phase as well as in the organic phase and may be added to the reaction mixture before, during or after mixing of the two phases.

The polycondensation reaction may be carried out at temperatures between l0 C. and the boiling point of the organic solvent used. If a diacid halide is employed which is sensitive to hydrolysis, it is desirable to cool the 3,505,289 Patented Apr. 7, 1970 reaction mixture to 0 C. or even lower so as to avoid this hydrolysis as much as possible.

Water is used as the solvent for the alkali diphenates and halogenated hydrocarbons, such as e.g. methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, sym-tetrachloroethane, methylchloroform, etc., are employed as common solvent for the diacid halide and the polyester to be formed by the reaction. Other water-immiscible organic solvents such as benzene, toluene, etc. can be used in association with the above mentioned solvents.

The highly linear polyesters of the present invention have an intrinsic viscosity of at least 0.4 and in most cases above 0.6 when measured in a solution of sym-tetrachloroethane at 25 C. and contain recurring groups of the following general formula:

radicals, and wherein R represents a divalent radical selected from the group consisting of ether radical, tertiary amino radical, carbonyl radical, thio radical, sulfoxide radical, sulfone radical, alkylene group, alkylidene group, alkyl substituted alkylene group, aryl substituted alkylene group, halogen substituted alkylene group, haloalkyl substituted alkylene group, alkyl and aryl substituted alkylene group, cycloalkylidene group, two alkylene groups bonded together by a radical selected from the group consisting of aryl, tertiary amino radical, ether radical, carbonyl radical, thio radical, sulfoxide radical and sulfone radical.

According to a preferred embodiment arylene is selected from the group consisting of phenylene and naphthylene including organic substituents therein selected from the group consisting of halogen and alkyl.

In the case where the highly linear polyesters are copolyesters, the structural units can be represented by the following general formula:

boxylic acid the copolyesters contain structural units of the following general formula LlJ.

wherein A, B, R and R" have the same significance as above and wherein A is taken from the group consisting of oxygen and sulfur and mand n are whole numbers.

In the polycondensation reaction according to the invention alkali diphenates are used which are obtained by dissolving diphenols in water in the presence of equivalent amounts of alkali hydroxides such as sodiumor potasnonr 1 F X Ar 1 L l l. Lam. Lari Herein Ar represents an aromatic group such as phenylene, biphenylene, naphthylene, etc. X can be an alkylene or an alkylidene group such as methylene, ethylene, propylene, ethylidene, propylidene, isopropylidene etc. X can also be one or more alkylene or alKylidene groups bonded together by an aromatic radical, by a tertiary amino radical, by an ether radical, by a carbonyl radical, by a radical containing sulfur such as a sulfide, a sulfoxide, a sulfone radical etc. Moreover X can be a cycloaliphatic group, or a radical containing sulfur, such as a sulfide (S), a sulfoxide (SO-) or a sulfone (SO group, an ether radical (O), a carbonyl radical (CO), or a tertiary amino (N(Alk)).

In the formula R represents hydrogen, alkyl (methyl, ethyl etc.), aryl (phenyl, naphthyl etc.), aralkyl (benzyl, ethylphenyl etc.), alkaryl or a cycloaliphatic radical, and all these radicals can be substituted by halogen. Y represents halogen, a substituent such as nitro, a radical R a radical R wherein R has the same significance as R above; n and m which are the same or ditferent integers may vary from 0 to the number of unsubstituted carbons on Ar or on X; p is an integer at least equal to 1; q is 0 or 1 and r is an integer which may be 0 if q also is 0.

If in the diphenols according to the formula, more than one substituent Y is present, the substituents may be the same or dilferent. The foregoing remark is also applicable to the substituent R When q is nought and 2' different from nought, the aromatic nuclei are directly bonded to each other.

The hydroxyl groups and the substituents Y of the aromatic nuclei may occur in the ortho-, metaor parapositions.

The following compounds are examples of diphenols the alkali diphenates of which can be used for preparing polysulfonates according to the invention:

OII

bis- 4-hydroxyphenyl methane bis- 4-hyd roXy-3-rnethylphenyl) methane bis-( 4-hydroxy-3,S-dichlorophenyl methane bis- (4-hydroxy-3,S-dibromophenyl methane bis- (4-hydroxy-3,5 difluorophenyl) methane bis- 4-hydroxyphenyl) ketone bis- 4-hydroxyphenyl) sulfide bis- (4-hydroxyphenyl) sulfone bisl-hydroxyphenyl) ether 1 l-bis- (4-hydroxyphenyl) ethane 2,2-bis- (4-hydroxyphenyl) propane 2,2-bis- (4-hydroxypheny1) butane 2,2-bis- (4-hydroxyphenyl l-methyl) pentane 2, 2-bis- 4-hydroxy-3 methylphenyl) propane 2,2-bis- (4-hydroxy-3-chlorophenyl prop ane 2,2-bis- (4-hydroxy-3,S-dichlorophenyl propane 2,2-bis- 4-hydroxy-3,5dibromophenyl) propane 2,2-bis- 4-hydroxynaphthyl) propane bis- (4-hydroxyphenyl) phenylmethane bis- 4-hydroxyphenyl) phenylmethylmethane bis- (4-hydroxyphenyl) diphenylmethane bis- 4-hydroxyphenyl) 4-methylphenyl) rnethane l, 1 bis- 4hydroxyphenyl) -2,2,2-trichloroethane bis- (4-hydroxyphenyl 4-chlorophenyl rnethane 1, l-bis- 4-hydroxyphenyl cyclohexane 1, l-bis- 4-hydroxyphenyl) 3-methylphenyl propane bis- 4-hydroxyphenyl cyclohexylmethane 4,4-dihydroxydiphenyl 2, 2 -dihydroxydiphenyl dihydroxynaphthalencs such as 2,6-dihydroxynaphthalene hydroquinone resorcinol 2,6-dihydroxytoluene radical 2,fi-dihydroxychlorobenzene 3,6-dihydroxytoluene, etc.

The diacid halides of the invention can be obtained e.g. by reaction of the respective aromatic disulfonic acids or dicarboxylic acids with thionyl chloride.

The term diacid halides of aromatic disulfonic acids is intended to refer to compositions of the general formula:

Hal.02s I}I" Jf JTY SOLHBJ V i )n' ip I iq' i ')n. |1-' V wherein Hal stands for halogen such as chlorine or bromine and wherein the symbols Ar, X, Y, R' n, m, p, q, r have the same significance respectively as Ar, X, Y, R n, m, p, q, r above.

'As aromatic disulfohalides which can be used in the polycondensation reaction according to the invention are mentioned among others the following disulfochlorides:

l,4-benzene-disulfochloride 1,3benzene-disulfochloride 1,Z-benzene-disulfochloride 2,4-toluene-disulfochloride 2,7-naphthalene-disulfochloride 4,4'-diphenyl-disulfochloride 4,4'-diphenylether-disulfochloride 4,4-diphenylmethane-disulfochloride 4,4'-diphenylsulfone-disulfochloride 3,3'-diphenylsulfone-disulfochloride 2,2-bis-(4-chlorosulfonylbenzyl)propane 4,5 dichloro- 1,3benzene-dis-ulfochloride 4,6-dich1oro-1,3benzene-disulfochloride 4,5,6-trichloro-l,3benzenedisulfochloride.

As is said above the diacid halides of aromatic dicarboxylic acids may be partly replaced by one or more diacid halides of dicarboxylic acids.

As diacid halides of dicarboxylic acids there can be used phosgene, thiophosgene and diacid halides of the general formula:

HalEZ-("3Ha1 wherein Hal represents chlorine or bromine and wherein Z represents one of the folowing radicals:

--(I'I}R1 ArAr ArX-Ar l 2)m 1 2)m (CR1R2) m" 1 2) m In this list of possible Z radicals the symbols have the following significance:

Ar is an arylene radical such as a phenylene or naphthylene radical, substituted (in ortho-, metaor paraposition) or not by alkyl or halogen;

R and R are hydrogen, alkyl or aryl;

X is one of the following radicals: -CZ Z CO-, O, S-, HSO, AO wherein Z and Z which are the same or different are hydrogen, alkyl, aryl or wherein Z and Z form together a cycloaliphatic ring;

n is an integer from 1 to 20 and The symbol indicates hydrogenation, either wholly or in part of an aromatic nucleus, of which the free bonds are in the 1,1-, 1,2-, 1,3- or 1,4-position.

As diacid halides of dicarboxylic acids which may be used according to the invention we mention among others the following diacid chlorides:

phosgene thiophosgene terephthaloylchloride isophthaloylchloride phthaloylchloride sebacoylchloride adipolychloride 4,4'-diphenylether dicarboxylic acid chloride (4,4-dihydroXydiphenyl-2,2-propane) -bischloroformate ethyleneglycolbischloroformate.

The diacid halides of aromatic disulfonic acids or of dicarboxylic acids may be, either in part or wholly, replaced by one or more diacid halides of aromatic monocarboxysulfonic acids of the general formula:

wherein Hal represents halogen such as chlorine and bromine, and wherein Ar represents an arylene group such as phenylene or naphthylene, or phenylene or naphthylene of which one or more of the hydrogen atoms of the aromatic nuclei have been substituted yat least one radical of the group consisting of alkyl and halogen.

As diacid halides of aromatic mono-carboxysulfonic acids we especially mention among others:

benzoylchloride-m-sulfochloride benzoylchloride-p-sulfochloride' benzoylchloride-o-sulfochloride, and 1,2-sulfonaphthoic acid.

According to the process of the invention the polycondensation of diphenates and diacid halides is carried out in the presence as catalysts of minor amounts of one or more compounds selected from the group consisting of quaternary ammonium compounds, tertiary sulfonium compounds, quaternary phosphonium compounds and quaternary arsonium compounds.

As quaternary ammonium compounds we mention among others:

trimethylbenzylammoniumchloride triethylbenzylammoniumhydroxide triethylbenzylammoniumchloride.

Examples of convenient tertiary sulfonium compounds are among others:

S,S'-p-xylylene-bis-(dihydroxyethylsulfoniumbromide) hexamethylene-S,S-bis-dimethyl-1,6-disulfoniumbromide tribenzylsulfonium hydrogensulfate.

In principle, any quaternary phosphonium compound can be used as catalyst; preferably, however, those which are soluble in water and/ or in the organic solvent wherein the polycondensation is carried out. Specific quaternary phosphonium compounds which can be used are e.g.:

triphenylmethylphosphonium iodide triphenylbenzylphosphonium chloride p-xylylene-bis-(triphenylphosphoniurnchloride) p-Xylylene-bis-(triethylphosphoniumbromide) tetraethylphosphoniumbromide triethyloctadecylphosphoniumiodide phenylethylpentamethylene phosphonium acetate bis- (triethylphosphoniumacetate) -1,4-butane and many others e.g. those mentioned in the book by Kosolapofi entitled: Organophosphorous compounds (John Wiley and Sons, New York, 1950), pp. 86-94.

Suitable quaternary arsonium compounds are e.g. found in the publications of A. Michaelis, Ann. Chem. 321, 141-248 (1902); and F. F. Blicke et al. J.A.C.S. 60, 421 (1938), 61, 89 (1939) and 63, 1493 (1941).

We mention among others:

triphenylmethylarsoniumiodide triphenylmethylarsoniumhydroxide triphenylethylarsoniumiodide triphenylhydroxyethylarsoniumchloride.

Due to the fact that the polysulfonates of the invention are thermoplastic, they can be worked up from the melt into useful shaped articles by applying fabrication techniques known in the art such as pressing, moulding or vacuum-forming.

It is a further advantage of the present invention that it provides for highly polymeric linear polysulfonates which are insoluble in low boiling solvents. Depending upon the special chemical structure of each of the polysulfonates involved, they are soluble in at least one halogenated hydrocarbon such as methylene chloride, chloroform, 1,2-dichlor0et hane, sym-tetrachloroethane, methylchloroform, 1,1,2-trichloroethane, etc. Most of the polysulfonates according to the invention, however, are soluble in more than one of the above-mentioned halogenated hydrocarbons, and are moreover soluble in orther solvents such as benzene, toluene, dioxane, tetrahydrofurane, etc.

From solution in methylene chloride or sym-tetrachloroethane the polysulfonates can be cast into colorless transparent films. The values of the mechanical properties are situated between the following ranges according to the particular chemical structure:

Tensile strength, kg./sq. mm.69

Yield strength, kg./ sq. mm.5-7

Elongation at break, percent26 Modulus of elasticity, kg./ sq. mm.240-320 Upon stretching the films, the mechanical properties can be greatly enhanced. Noteworthy is the elongation at break which after stretching reaches values as high as Softening temperatures of polysulfonate films were determined by measuring as a function of temperature the elongation of film strips of fixed dimensions subjected to a constant load of 0.17 kg./sq. mm. The temperature range where an appreciable rise in elongation of the films is observed, is indicated in the tables as the softening point. It must be emphasized that these temperatures have only a comparative value since they are more or less dependent on the method of measurement. However, they are indicative of the glass transition temperature of the polymer, which is situated in the same temperature range. This has been verified for instance in the case of polymer 18 (see following table) where a glass transition temperature of 112 has been determined dilatometrically while for the softening point a range of 115-116 is noted.

In the following table there are assembled the softening point, the solubility and the intrinsic viscosity [1 of a series of representative polysulfonates.

provides for polysulfonates from which films can be produced which possess a high dimensional stability when exposed to varying temperatures and varying humidities.

Softening Solu- No. t-emp., C. bility l Poly4,4-diphenyldisulfonate from- 1 B is- (4-hydroxyphenyl)-methane 111-118 D 0. 40 2 1,1-bis-(4-hydroxyphenyl)ethane. 100-111 D 1. 1 3 2,2-bis-(4-hydroxyphenyD-propane 160-165 A-E 0. 5-2. 7 4 2,2-bis-(4-hydroxyphenyD-hutane 134-140 A-E 1. 6 5 2,2-bis-(4-hydroxyphenyl)-(4-methyl)-pentane 147-150 A-E 0. 50 6 1 ,1-bis- (4-hydroxyphenyl)-cyclohexane 108-112 A 1. 1-1. 6 7 Bis-(4-hydroxyphenyl)-pheny1methaue 155-160 11-15 1. 5 8 Bis-(4-hydroxyphenyD-phenylmethyimethane 162-169 A-E 1. 0 9 Bis-(4-hydroxyphenyl)-sulfone D 0. 10 Bis- (4-hydroxy-3-methylphenyl) -methane 114-120 D 0. 6 11 2,2-bis(4-hydroxy-3-methylphenyD-propane 132-136 11-15 1. 4 12 1 ,1-bis-(4-11ydroxy-B-methylphenyl)-eyelohexane. 146-151 A-E 1. 4 13 r. 2,2-bis-(4-hydroxy-3,5-dichlorophenyl)-propane 197-200 11-15 1. 7 14 2,2-bis-(4-hydroxy-3,fi-dibromophenyD-propane .1 200-207 A-E 1. 7

Poly-1,4'-dipheuyletherdisulfonate from- 5 B is- (4-hydroxypheuyl) -methane 1 97-100 A-E 0. 80 6 1 ,1-bis- (4-hydroxyphenyl)-ethane 1 100-107 A-E 0. 17 2,2-bis-(4-hydroxyphenyl)-propane 118-120 11-15 1. 0 18 2,2-bis-(4-hydroxyphenyl)-butane 111-116 A-E 0. 70 19 A- 2,2-bis-(4-hydroxyphenyl)-pentane 106-111 11-11 0. 70 0 1,1-bis-(4-hydroxyphenyl)-eyelohexane. 120-125 A-E 1. 2 1 Bis-(4-hydroxyphenyl) -phenylmethaue 116-120 A-E 0. 70 22 Bis-t i-hydroxyphenyl)-phenylmethylmethane 130-138 A-E 6 3 Bis- (at-hydroxyphenyl)-dipheny1methane 126-131 A-E 0. Bis-(4-hydroxyphenyD-sulfone 140-142 11-13 0. 2,2-bis- (4-hydroxy-3methylphenyD-prop 72-78 A-E 0. 2,2-bis-(4-hydroxy-3,5-diehlorophenyl)-propane 142-151 A-E 2. 5 2,2-bis- (4-hydroxy-3,5-dibromoph enyl) -propane 156-164 A-E 1. 05

Poly-4,4-diphenylmet-hanedisulfonate from Bis-(4-hydroxyphenyD-methane- 110-114 A-E 1. 5 1,1-bis- (4-hydroxyphenyD-ethane D 1. 3 2,2-bis-(4-hydroxypheuyl)-pr0pa1 6 A-E 0. 2,2-bis-(4-hydroxypheuyl)-butane A-E 0. 75 3,3-bis-(4-hydroxyphenyl)-pentane -104 A-E 0. 7 1,1-bis-(4-hydroxyphenyl)-eyclohex 82-04 A-E 0. 4 Bis-(4-hydroxyphenyD-ph enylmethane 133-134 11-11 95 Bis-(4-hydroxyphenyl) -phenylmethylmethan 131-132 A-E 0. 75 1315- (4-hydroxyphenyl) -sulfone 126-130 A-E 0. 30 Poly-2,4-toluenedisulfonate from- 7 2,2-bis- (4-hydroxyphenyl) -prop ane 84 A-E 0. 60 38 Bis- (4-hydroxyphenyl) -phenylmethylmethan 106-112 11-15 0. 50 9 2,2-bis-(at-hydroxyphenyl-3,5-dichlorophenyl)-propan -156 A-E 0. 80 40 2,2-bis- (4-hydroxyphenyl-3,5-dibromophenyl) -propane. -173 A-E 0. 80

Poly-1,3-benzenedisulfonate from- 41 2,2-bis-(4-hydroxyphenyD-propane 49 11-13 0 80 42 2,2-bi5-(4-hydroxyphenyl-3,5-dichloropheny1)propane 1 0- 7 A-E' 0 43 2,2-bis-(4-hydroxyphenyl-3,S-dibromophenyl) -propane 149-152 A-E 0. 80

Poly-3,3-diphenylsulionedisulfonate from- 4 2,2-bis- (4-hydroxyphenyD-propane 100-10 A-E U- 90 1 A =meth ylenechloride; B 1,2-dieh1oroethane; C 1 ,2,2-triehloroethane; D =sym-tetrachloroethane; E tetrahydroiurane.

Intrinsic viscosity, d1. /g., measured in sym-tetrachloroethane.

It is a particular advantage of the present invention that it provides for a polycondensation process according to which aromatic polysulfonates can be produced which possess an exceptionally high-molecular Weight as indicated by their intrinsic viscosities ranging from 0.4 to

2.5 determined in dichloroethane or tetrachloroethane solution.

In this respect the aromatic polysulfonates produced according to the process of the present invention possess outstanding properties relative to the formerly proposed polysulfonates. From the polysulf-onates produced according to the process of the present invention, moreover, films can be obtained which advantageously can be used for special purposes e.g. as photographic film-base, the

polymers showing an intrinsic viscosity greater than 0.5

and in many cases greater than 1.

low boiling solvents or by extruding them from the melt The films or fibers prepared from the polysulfonates acrding to the invention by casting them from solution in ed not necessarily be stretched and heat set in order give them useful properties since the unstretched films show good mechanical properties. If desired, however, the strength of shaped articles such as films and fibers epared from the polysulfonates of the invention can 70 It is a particular advantage of our invention that it These properties, which are to be ascribed to the high softening points and the low water-absorption of the polysulfonates make them particularly useful for the manufacture of dimensionally stable photographicfilm base. Dimensional stability is an important requirement for a film support onwhich light-sensitive emulsions etc., for graphic art work are to be coated.

A further advantage of the present invention is that it provides for polysulfonates which can be transformed from the melt or from solutions into fibers showing good textile properties. I

It has further been found that the polysulfonates of the present invention possess very interesting electrical properties so that they can advantageously be used in electrophotographic materiais.

The invention includes polysulfonates obtained by reacting a mixture of two or more of the specified diphenates with one or more of the specified diacid halides of aromatic disulphonic acids or mixtures of two or more of these diacid halides with one or more of the said diphenates.

The invention further includes polymers obtained by using a mixture of one or more of the above-mentioned bisphenates with diphenates such as e.g. those derived from hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, bis- (4-hydroxylphenyl -sulfone, bis- (4-hydroxyphenyl) ket-one etc., or by using a mixture of one or more of the above-mentioned diacid halides of aromatic disulfonic acids with diacid halides of dicarboxylic acid such as specified above.

The invention furthermore includes polysulfonates obtained by replacing the mixture of one or more diacid halides of aromatic disulfonic acids and of one or more diacid halides of dicarboxylic acids, either Wholly or in part by one or more diacid halides of aromatic monocarboxy-sulfonic acids.

In the latter cases we are concerned with copolycarboxylatesulfonate polymers and we wish to point out the variety of final condensation products which can be obtained.

Moreover, there exist still further possibilities for causing the type of the copolycarboxylate-sulfonate to vary. In a random polycondensation, the structural units are spread in a statistical way over the polymer chain. By another method, however, a certain ordering in the sequence of the structural moieties in this polymer can be obtained. Instead of reacting the three reagents simultaneously, we can for instance start from a solution or dispersion in an organic solvent of the aromatic disulfochloride only. The polycondensation is carried out by addition of an aqueous solution of an alkali diphenate and of the catalyst.

After a more or less long time lapse the solution or dispersion of the dicarboxylic acid chloride is added to the reaction mixture and the polycondensation is further effected. In this case the so called block copolycondensates are obtained in which the structure is supposed to consist mainly of more or less long sequences of sulfonate moieties, followed by more or less long sequences of carboxylate moieties. In the same way, the dicarboxylic acid chloride can first be caused to react with the alkalidiphenate and only after a more or less long reaction time the aromatic disulfochloride can be added By starting from mixtures of the different reagents, the different blocks can, of course, be varied still further and consequently also the properties of the copolycondensate finally obtained can be varied.

In all these variants, the amounts of the different recocondensates the high weakening point of the pure polysulfonates is accompanied by a sufliciently high elongation at break. It follows that films cast from their solution are tough and do not show any tendency to craze. Stretching of these films, however, is a means of further improving the mechanical properties. The optimum properties of the non-stretched films evidently depend on the kind of the mutual proportions of the reagents used and the optimum composition can for each case be experimentally determined in an easy way.

The copolycarboxylate-sulfonates according to the present invention are in most cases soluble in chlorinated aliphatic and aromatic hydrocarbons and in some cases also in tetrahydrofurane and in dioxane.

The properties of films cast from solutions of copolycarboxylate-sulfonates, of course, depend on the chemical nature of the recurring moieties and of the relative proportion of carboxylate bonds (COO) and sulfonate bonds (-SO O-) in the polymer chain. The proportion of the latter whereby the most desired mechanical properties are obtained can be experimentally determined in an easy way for each type of copolymer.

For example, for the copolycarboxylate-sulfonate prepared from bisphenol A and a mixture of 4,4'-diphenyldisulfochloride and bisphenol-A-bis-chloroformate, the molar proportion of disulfonic acid chloride and bischloroformate can be modified at the start of the reaction and the mechanical properties of the films can be determined for each copolymer thus obtained.

.In the following table the properties of these copolymers are compared with those of the homopolymers. In the first column the molar proportion of the 4,4-diphenyldisulfochloride to the 2,2-bis(4-hydroxyphenyl)-propane bischloroforrnate used in the preparation is given. Since the polycondensation proceeds with a yield of about 100%, this molar proportion corresponds to the molar proportion in the polymer chain of the recurring moieties having the following chemical structure:

CH 8 CH A TABLE 1 Tensile Elasticity Elongation Softening transition Molar proportion, strength, modulus, at break, temperature, temper- Cold Moicty AzMoiety B kgJsq. mm. kgJsq. mm. percent 0 ature, 0. drawing Polymer No.

1 The mechanical properties were determined on film strips of the following dimensions, length between clamps mm. width 2 The glass transition temperature has been determined by measuring the enthalpy of the polymer as a function of temperatureagents must be chosen in such a Way that the total amounts of acid chlorides, i.e. the amounts of sulfochloride together with the amounts of carboxylic acid chloride, correspond substantially stoichiometrically to the amounts of the bisphenols used. However, high molecular weight products can be obtained if a slight excess of acid chlorides or alkalibisphenates is present.

The properties of the copolycarboxylate-sulfonate obtained will, of course, depend to a large extent on the way in which the aqueous solution of the alkalibisphenate is added to the acid chloride solutions or dispersions. Generally it can be said that with a suitable choice of It clearly appears from this table that the properties of the copolycondensates according to the present invention strongly depend on the molar proportion of the sulfonate bonds (SO O) to the carboxylate bonds the molar proportions of the different reagents for the ible films which on rough handling do not show a tendency to craze. This unfavorable property only appears when the elongation at break in the copolymers cited is less than 6% It is also printed out that the films showing the property which in the literature is called cold drawing do not show a tendency to craze by a rough handling of the film.

It is also printed out that Polymer No. 1 contrary to the others shows a brittle failure at room temperature while the others show a ductile failure. For the difference between the twotypes of break phenomena we refer to: Die Physik der Hochpolymeren von H. A. Stuart, Band 1V, pages 174-176, Springer-Verlag, Berlin 1956'.

Once the film breaks with a ductile failure, there is for the application as a photographic support of graphic lightsensitive material little difference whether the elongation at break is very high or not; this means the polymers 2 to 6 possess about the same practical value if judged on their break phenomenon. For many application fields and in particular for application as a photographic support an elasticity modulus which is as high as possible is of great importance. A high elasticity modulus involves an increase of the dimensional stability of photographic films manufactured on dimensionally stable supports. Practically for all applications a high sheet softening temperature is of very great value. The higher this softening temperature, the better will be the dimensional stability of the sheets when the environmental temperature increases.

It further clearly appears from the table that glass transition temperature for the copolymer No. 3 (prepared according to Example 39) is practically as high as for the hornopolysulfonate (Polymer No. 1).

From all these data the favourable properties of the copolymers described in this invention are clearly shown. According to the uses for which the new copolymers are intended these improved properties can be employed to advantage.

The same considerations can be held for each series of copolymers described in the present invention. The above series was chosen as an example for denoting the exceptional properties of the copolymers.

EXAMPLE 1 18.35 g. of 4,4-diphenylether-disulfochloride, 0.25 g. of triethylbenzyl ammonium chloride and ccs. of methylene chloride are successively brought into a three- 12 EXAMPLE 2 140.4 g. of 4,4'-diphenyl-disulfochloride, 4 g. of triethylbenzyl ammonium chloride and 800 ccs. of methylene chloride are successively brought into a three-necked three liter flask provided with a stirrer, a refluxer, a thermometer and a droping funnel. While stirring at a temperature of 20-25 C. a solution of 91.2 g. of 2,2-bis- (4-hydroxyphenyl)-propane, 32.5 g. of sodium hydroxide and 800 ccs. of water is dropwise added through the funnel within A of an hour. The reaction mixture is further stirred for 3 hours whereupon the polymer separates as a viscous mass. The supernatant water is decanted and the residue is washed for hour with 800 ccs. of Water whilst strongly stirring. The product is obtained by pouring out the viscous mass in hot water and drying at 100 C. Intrinsic viscosity of this polysulfonate measured in tetrachloroethane: 1.5 dl./ g. Softening point: 150l60 C.

The polysulfonate obtained corresponds to the formula:

EXAMPLE 3 3.67 g. of 4,4-diphenylether-disulfochloride, 0.05 g. of triethyl-benzyl ammonium chloride and 12.5 ccs. of methylene chloride are successively brought into a threenecked 100 ccs. flask provided with a stirrer, a rcfluxer and a dropping funnel. While stirring at room temperature a solution of 2.76 g. of bis(4-hydroxyphenyl))- phenylmethane and 19.8 ccs. of sodium hydroxide solution 1.0267 N is dropwise added through the funnel, within A hour. The reaction mixture is further stirred for 2 hours whereby the polymer separates as a viscous mass. The supernatant water is decanted and the residue is washed for hour with 20 ccs. of water while strongly stirring. The product is obtained by pouring out the viscous mass in hot water and drying at 100 C. Intrinsic viscosity measured in 1,2-dichloroethane: 0.6 dL/g. Softening point: 125 C.

The polysulfonate obtained corresponds to the formula:

necked half liter flask provided with a stirrer, a refluxer and a dropping funnel. While stirring at room temperature a solution of 11.4 g. of 2,2-bis(4-hydroxyphenyl)- propane and 99 ccs. of sodium hydroxide 1.0267 N is dropwise added through the funnel within half an hour. The reaction mixture is further stirred for 2 hours whereupon the polymer separates as a very viscous mass. The supernatant'water is decanted and the residue is Washed for hour with 100 ccs. of water while strongly stirring. The product is obtained by pouring out the viscous mass in hot water and drying at 100 C. Intrinsic viscosity measured in 1,2-dichloroethane: 1.0 dl./g. Softening point: 110 C.

The polysulfonate obtained corresponds to the formula:

EXAMPLE 4 3.67 g. of 4,4-diphenylether-disulfochloride, 0.05 g. of triethylbenzyl ammonium chloride and 15 ccs. of methylene chloride are successively brought into a threenecked ccs. flask provided with a stirrer, a refluxer and a dropping funnel. While stirring at room tempera ture a solution of 3.52 g. of bis-(4-l1ydroxyphenyl)-diphenylmethane, 9.5 ccs. of sodium hydroxide solution 2.14 N and 2.5 ccs. of dioxane is dropwise added through the funnel within A hour. After still adding 20 ccs. of water, the reaction mixture is further stirred for 2 hours whereby the polymer separates as a viscous mass. The supernatant water is decanted and the residue is washed for Mr hour with 50 ccs. of water while strongly stirring.

13 14 The product is obtained by pouring out the viscous mass 140-142 C. The film shows a tensile strength of 7.3 in hot water and drying at 100 C. Intrinsic viscosity kg./sq. mm. an elongation at break of 3% and a modulus measured in 1,2-dichloroethane: 0.46 dL/g. Softening of elasticity of 300 kg./sq. mm. point: 130 C. The polysulfonate obtained corresponds to the formula:

The polysulfonate obtained corresponds to the for- EXAMPLE 7 mula: 9.12 g. of 2,2-bis-(4-hydroxyphenyl)-propane, 84 ccs.

EXAMPLE 5 of sodium hydroxide solution 0.963 N, 0.4 g. of triethyl- Y benzyl ammonium chloride and ccs. of 1,1,2-trichloro- 3.51 g. diphenyl-p,p'-disulfochloride (0.01 mol), 0.1 ethane are successively brought into a three-necked 250 g. of triethylbenzyl ammonium chloride, 3.06 g. of biS- ccs. flask, provided with a stirrer and a dropping funnel. (4-ihydr xy-2, im hy p y n 1 f While stirring at room temperature, a solution of 11 g.

mihylene o de are successively brought into a threeof benzene-1,4-disulfochloride into 35 ccs. or 1,1,2-trinecked 250 ccs. flask, provided with a stirrer and a chloroethane is dropwise added through the dropping dropping funnel. While stirring at room temperature, funnel within 15 minutes. After the addition of the diacid 22. ccs. of sodium hydroxide solution 0.891 N is dropchloride solution, the reaction mixture is stirred at room wise added through the dropping funnel within 10 mintemperature for another 30 min., whereby the polymer utes. After the addition of the alkali solution, the reacseparates as a viscous mass. The supernatant aqueous tion mixture is stirred at room temperature for another layer is decanted and the residue washed two times with 60 min., whereupon a thick viscous emulsion is obtained. 30 ccs. of water, while strongly stirring, whereupon the The polymer emulsion is diluted with 50 ccs. of methylpolymer solution is diluted with 50 cos. of methylene enechloride. The polymer is isolated by pouring out the chloride. The polymer is isolated by pouring out the polymer solution in ethanol, washing the precipitate with polymer solution in ethanol, and drying the precipitate water and ethanol and drying the precipitate at 110 C. at 120 C. The intrinsic viscosity was measured in sym.- The intrinsic viscosity was measured in sym.-tetrachloro tetraohloroethane and found to be 1.46 dl./g. A film ethane and found to be 0.4 dl./ g. The polymer is only cast from a methylene chloride solution shows a softenpartially soluble in methylene chloride but soluble in ing temperature of 140 C.

sym tetrach1oroethane The polysulfonate obtained corresponds to the formula:

CH; Q- Q Q CH3 x L J The polysulfonate obtained corresponds to the for- Emu 'IPLE 8 mula; 2.264 g. of 2,2-bis-(4-hydroxyphenyl)-propane, 19.8

I- CH3 CH3 1 L i (3H3 Ha |X EXAMPLE 6 ccs. of sodium hydroxide solution 1.017 N, 0.1 g. of d l H 001 mol triethylbenzyl ammonium chloride and 5 ccs. of meth- 3i g s i i gggg g g gg f g N, 01 ylene chloride are successively brought into a threeof triethylbenzyl ammonium chloride are successively necked 250 ccs. flask, provided with a stirrer and a dropbrought into a three-necked 250 ccs. flask, provided with R funnel. While Stirring at room temperature, a $0111 a sti fer and a dropping funnel. Whilst tirring and at 11011 Of g. Of S111fOI1-In,m'-dlSUlfOCh]Ol'ldC room temperature, a solution of 3.67 g. of diphenyletherin 25 cos. of methylene chloride is dropwise added p,p'-disulfochloride into 15 ccs. of 1,1,2-trichloroethane through the dropping funnel within 10 minutes. After the is'dropwise added through the dropping funnel within 10 addition of the diacid chloride solution, the reaction mixminutes. After the addition Of the diacid chloride SOlllture is tirred at room temperature for another 2 hours, 9 the reaction mixture 15 surfed t room temperature whereby the polymer separates as a viscous mass. The for an th r 2 hours whereupon the P y Separates supernatant aqueous layer is decanted and the residue 'as' a viscous mass. The supernatant aqueous layer is decanted and the residue washed two times with 20 ccs. of water, whilst strongly stirring, whereafter the polymer solution is diluted with 50 ccs. of 1,1,2-trichloroethane. methglenelchlondel' [1.116 Polymer 18 Isolated The polymer is isolated by pouring out the polymer soluy Pom-mg i t 6 Po ymer so P h f P tion in ethanol, and drying the precipitate at 1100 c. The ing the precipitate at 70 C. The intrinsic vlscosity was intrinsic viscosity was measured in sym.-tetrachloroethane measured sym'tetrachloroethane and founfl to be d found t b 0,62 dL/g, A fil t fr a th- 0.85 dl./ g. A film cast from a methylene chloride soluylene chloride solution shows a softening temperature of tion shows a softening temperature of C.

washed two times with 20 ccs. of water, whilst strongly stirring, whereupon the polymer solution is diluted with 8,505,289 16 The polysulfonate obtained corresponds to the for- EXAMPLE 11 mula' CH 3.51 g. of 4,4'-diphenyl-disulfochloride, 0.05 g. of tr-i- 3 ethylbenzyl ammonium chloride and ccs. of dichloro- O methane, are successively brought into a three-necked CH; 5 100 ccs. flask provided with a stirrer, a refluxer and a x dropping funnel. While stirring at room temperaturea solution of 2.68 g. of l,l-bis (4-hydroxyphenyl) cyclohexane, 9.5 ccs. of sodium hydroxide 2.14 N, 4 ccs.:of

dioxane and 5 ccs. of water is dropwise added to the funnel within A hour. After adding 20 ccs. of water,

EXAMPLE 9 3.65 g. of diphenylmethane-p,p'-disulfochloride (0.01 mol), 0.1 g. of triethylbenzyl ammonium chloride and 15 ccs. of methylene chloride are successively brought the reaction mixture is further stirred for 2 hours whereby into a three-necked 250 ccs. flask, provided With a stirrer the polymer separates as a viscous mass. The supernatant and a dropping funnel. While stirring at room tempera- Water is decanted and the residue is Washed'for hour ture, a solution of 2 g. of bis-(4-hydroxyphenyl)-meth- 15 with 50 ccs. of water while strongly stirring. Theprodngzt ane in 18.6 ccs. of sodium hydroxide solution 1.089 N is obtained by pouring out the viscous mass in hot Water is dropwise added through the dropping funnel within 10 and drying at 100 C. Intrinsic viscosity measured jin minutes. After the addition of the bisphenol solution, 1,2-dichloroethane: 0.5 dL/g. Softening point: 155 ..C.

the reaction mixture is stirred at room temperature for The polysulfonate obtained corresponds to the formula:

another 2 /2 hours, whereby the polymer separates as EXAMPLE 12 i h a viscous mass. The supernatant aqueous layer is de- I z canted and the residue washed two times with 50 ccs. 1 gof ,4-d1pheny1-d1sulfO0h1 r 5 gf triof Water, while strongly stirring, whereafter the polymer ethy b y ammonium Chlorlde d 206681 fm hviiifie solution is diluted with ccs. of methylene chloride. The 30 chloride are successively brought into a fi- 'km polymer is isolated by pouring out the polymer solution ccs. flask provided with a stirrer, a refiuxer and a in methanol, and drying the precipitate at 100 C. The dropping funnel. While stirring at room temperature a intrinsic viscosity was measured in syrn.tetrachlor0 solution of 2.42 g. of 2,2-bis-(4-hydroxyphenyl)-butahe ethane and found to be 1.5 dL/g. A film cast from a and 19.8 ccs. of sodium hydroxide solution 1.0 267' N is methylene chloride solution shows a softening tempera- 35 dropwise added through the funnel within hour. The

ture of C. reaction mixture is further stirred for 2 hours whereby The polysulfonate obtained corresponds to the forthe polymer separates as a viscous mass. The supernatant mula: water is decanted and the residue is washed 'for A hour EXAMPLE 10 with 20 ccs. of water while strongly stirring. The prod- 351 g. of 4,4'-diphenyl-disulfochloride, 0.05 g. of tri- M is obtained y pouring out the viscous mass in h ethylbenzyl ammonium chloride and 20 ccs.. of methylene 45 Water aI 1d y g at S C viscosity measured chloride are successively brought into a three-necked m llz'dlchlofoethaflei dL/g- P kl-li 100 ccs. flask provided with a stirrer, a refluxer and a The polysulfonate Obtaimd corresponds to the f mula:

N CH;

L l J dropping funnel. While stirring at room temperature a EXAMPLE 13 solution of 2.9 g. of bis- (4-hydroxyphenyl)-pheny1 methyl methane, 9.5 ccs. of sodium hydroxide solution 2.14 N and 10 ccs. of dioxane is dropwise added through the funnel within 4 hour. The reaction mixture is further stirred for 2 hours while the polymer separates as a viscous mass. The supernatant water is decanted and the residue is washed for hour with 50 ccs. of Water while strongly stirring. The product is obtained by pouring out the 7.02 g. of 4,4-diphenyl-disulfochloride, 0.2 g. of triethylbenzyl ammonium chloride and SO ccs. of methylene chloride are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel.-

0 While stirring at room temperature a solution of 7.32 g. of 2,2-bis-(4-hydroxy-3,S-dichlorophenyl)-propane and 39.8 ccs. of sodium hydroxide solution-1.017 N is drop:

o wise added through the funnel within 10 min-The, reacvisco s m s n h0t Wat@f f drying at 100 Intrlnslc tion mixture is further stirred for-1V2 hours whereby the viscosity measured 1n 1,2-dichloroethane: 0.5 dl./g. Soft- 65 polymeij Separates as a viscous mass, Th supernatant ening point: C. Water is decanted and the residue is washed with water The polysulfonate obtained corresponds to the formula: until neutral while strongly'stirrin'g. The product is. ob-

17 18 tained by pouring out the viscous mass in hot water and mer separates as a viscous mass. The supernatant aqueous drying at 100 C. (solid flakes). Intrinsic viscosity measlayer is decanted and the residue washed two times with ured in 1,2-tetrachloroethane -.67 dl./ g. Softening point: 50 cos. of water, while strongly stirring, whereupon the 180190 C. polymer solution is diluted with 20 cos. of methylene The polysulfonate obtained corresponds to the formula: chloride. The polymer is isolated by pouring out the poly- C1 C1 I 3 l @-C $C L 1 3 J EXAMPLE 14 mer solution in boiling water, and drying the precipitate 3.67 g. of 4,4'-diphenylether-disulfochloride, 0.1 g. of at The intrlnsic viscosity was measured in y triethylbenzyl ammonium chloride and 20 ccs. of methtetrachloroethane and folmd to 8' A film Q ylene chloride are successively brought into athree-necked 15 from a methylene cchlorlde sollltlon Shows a q 250 fl k provided with a stirrer and a dropping f temperature of 100 C. and a modulus of elasticity of nel. While stirring at room temperature a solution of 3.66 330 kg/Sqg. of 2,2-bis-(4-hydroxy-3,S-dichlorophenyl)-propane and The Polysulfonate Obtamed corresponds to the 19.9 ccs. of sodium hydroxide solution 1.017 is dropwise mula:

added through the funnel within 10 min. The reaction CH3 mixture is further stirred for 1 hour whereby the polymer A I separates as a viscous mass. The supernatant water is de- O2S SO2 O 3 canted and the residue is washed with water until neutral J H C CH while strongly stirring. The flocky product is obtained after dilution with methylene chloride and precipitation in ethanol. Intrinsic viscosity measured in 1,2-tetrachloro- EXAMPLE 17 ethane: 2.5 dl./ g. Softening point: 140 C. 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.02 The polysulfonate obtained corresponds to the formol), 40.4 cos. of sodium hydroxide 1 N, 150 mg. of mula: triethylbenzyl ammonium chloride and 20 ccs. of water 01 01 I H3 I CH i ('31 a 21 i EXAMPLE 15 are successively brought into a three-necked 250 ccs. 2.89 g. of 2,4-toluene disulfochloride, 0.1 g. of trik m f Wlth a stirrer and a dropping ethylbenzyl ammonium chloride and 15 ccs. of methylene Whllst snmng and at room tefnpsramrei a Solutlon of chloride are successively brought into a three-necked 40 g'of1'chlorobemen?'24'd1su}fchlnde(002 mol) 250 ccs. flask provided with a stirrer and a dropping funmto of be.nz.ene 1S qropwlse added throlilgh the nel. While stirring at room temperature a solution of 5.44 dropPmg funnel. Wlthm 15 mmutes' After the addltlon of of 2,2 bis (4 hydroxy 3,idibromoPhenYl) propane the dlacid chloride solution, the reaction mixture is stirred and 19.9 ccs. of sodium hydroxide solution 1.017 N is at room temperature for another 2 hours whereby the dropwise added through the funnel within 10 min. The Polymer Separates as a Viscous mass- Supernatant reaction mixture is further stirred for 1% hours whereby alquwus .layer 18 decanted and resldue washefl i the polymer separates as a viscous mass. The supernatant tunes wlth of l m l stlmng water is decanted and the residue is washed with water whereafter the polymer Solutlon 4 wlth 50 until neutral Whilst strongly stirring. The fiocky product 9 methylene chlonde' i Isolated by Pour is obtained after dilution with methylene chloride and 50 mg out the polymer Solutlon bolhng Water: and

reci itat'on in ethanol. Intrinsic viscosit measured in ing the prcipitate at 100 The intrinsic viscosity was lteptracifloroethanez 0 88 d1. g softenigg point: measured in syun.-tetrachloroethane and found to be 0.02 C A film cast 5 methylene chloride has an dl./g. A film cast from a methylene chloride solution elastic; modulus of 310 kgjsq mm shows a softening temperature of 75 C. and a modulus t f of elasticity of 311 kg./ sq. mm. 52? Polysulfonate Obtamed corresponds to he or 55 The polysulfonate obtained corresponds to the formula: Br CH 1?! i l a... O2S- SO2O -C- O- l J Cl CH3 a CH3 Br Br EXAMPLE 16 Z EXAMPLE 1:;

2.75 g. of 1,3-benzene-disulfochloride, 0.1 g. of tri- 6- g- Of 1.3'dimethylbIlene-4:6'disulfochloride ethylbenzyl ammonium chloride and 20 ccs. of methylene (0 200 of triethylbenzyl ammonium 9 chloride are successively brought into a three-necked 250 ride and 20 ccs. of methylene chloride are successively cw fl k provided with a stirrer and a dropping funneL brought into a three-nefiked 250 flask, PYOVlded Wlth While stirring at room temperature a solution of 3.66 g.

a stirrer and a dropping funnel- W e Sti g a m of 2,2-bis-(4-hydroxy-3,S-dichlorophenyl)-propane and temperature, a soluti n f .5 gf Y Y- 20.5 ccs. of sodium hydroxide solution 1 N is dropwise phenyl)-propane (0.02 mol) in 40.4 ccs. of sodium hyadded through the funnel within 5 min. The reaction mixdroxide solution 1 N is dropwise added through the dropture is further stirred for 1 hour whereby the polymer ing funnel within 15 minutes. After the addition of the diseparates as a viscous mass. The supernatant water is deacid chloride solution, the reaction mixture is stirred at canted and the residue is washed with water. The product room temperature for another 30 min. whereby the polyis obtained by pouring out the viscous mass in hot water and drying at 100 C. (hard flakes). Intrinsic viscosity EXAMPLE 21 measured in 1,2-tetrachloroethaue: 0.96 dl./g. Softening point: 140147 C. A film cast from methylene chloride has an elasticity modulus of 345 kg./ sq. mm.

.The polysulfonate obtained corresponds to the formula:

A 250 ccs. flask, fitted with a stirrer, a thermometer and a dropping funnel, is filled with a mixture .of 3.51

g. of 4,4-diphenyl-disulfochloride, 0.1 g. of triethylbenzyl ammonium chloride and ccs. of methylene chloride. Whilst stirring, an aqueous solution of 2.56 g.

CH3 1 Y of bis-(4-hydroxy-3,S-dirnethylphenyl)-methane in 19.8

| ccs. of sodium hydroxide 1.043 N is added Within 15 'OZS O T minutes. After the addition of the bisphenate solution, 1 0H; t 10 the reaction mixture is stirred for another 60 minutes i C1 01 I whereupon the aqueous layer is decanted; the reaction mixture is subsequently washed two times with 100 ccs. EXAMPLE 19 of water, the water layer is decanted, the organic layer 702 g. of 4,4'-diphenyl-disulfochloride (0.02 mol), 0.2 r diluted with ccs. of methylene chloride and 100 ccs. g. of triethylbenzyl ammonium chloride and 40 ccs. of of methanol is added to the polymer solution, and the methylene chloride are successively brought into a threeprecipitate is isolated and dried. Yield: 5.2 g. The polynecked 250 ccs. flask, provided with a stirrer and a dropmer obtained can be represented by the following strucping funnel. While stirring at room temperature, a solutural formula:

[ i r a 1' L (3H3 (1H3 JX tion of 5.12 g. of 2,2-bis-(4-hydroxy-3-methyl)-propane The intrinsic viscosity was measured in sym.-tetra- (0.02 mol) and 40.3 ccs. of sodium hydroxide solution hl h d fo d to be 114 dL/g A 15% 1 i5 dronwise addd through PP f tion was made in methylene chloride and spread outwith nel within 10 minutes. After the addltion of the blS- a doctor blade on a glass plate. The resulting transparent phenol solution, the reaction mixture 15 stirred at room polymer film was dried at for 10 hours The temperature for another 21/2 hours whereby the polymechanical properties of the film, measured on an Inmer separates as a viscous mass. The supernatant aqueous layer is decanted and the residue washed two times with 50 ccs. of water, whilst strongly stirring, whereupon the polymer solution is diluted with 50 ccs. of i g? i y??? m methylene chloride. The polymer-is isolated by pouru 0 :2 ing out the polymer solution in methanol, and drying at re poerccnt the precipitate at 120 C. The intrinsic viscosity was Softenmg range 140 170 m asured in s m.-tetrachloroethane and found to be 1.4 if/g A fil yeast f a methylene hl i l i The elongation at break of the film obtained from this shows a softening temperature of 132l36 C. polysulfonate is the more unexpected since by using in stron tester were as follows:

The polysulfonate obtained corresponds to the formula: the production of the polysulfonates a bisphenate of a 1- CH3 i J CH3 CH3 X EXAMPLE 20 bisphenol of slightly different chemical composition such 3.51 g. of 4,4-diphenyl-disulfochloride 0.01 mol), asofablsphenmepresemed by hefmmula: 0.1 g. of triethylbenzyl ammonium chloride and 20 ccs. E CH3 (3113 of methylene chloride are successively brought into a three-necked 250 ccs. flask, provided with a stirrer and O C a dropping funnel. While stirring at room temperature, CH3 1 a solution of 2.28 g. bis-(4-hydroxy-3-methylphenyl) methane (0.01 mol) in 18 6 ccs. of sodium hydr x only an elongation at break of 3% of the unstretched 9 L089, 15 droPwlse added through drop polysulfonate films is measured. Also the use of bisping funnel W1th1n 10 minutes. After the addltion of the phenols having only one methyl group on each phenyl bisphenol solution the reaction mixture is stirred at room nucleus and without substituents on the central carbon temperature for another whereby the Polymer 60 atom results in a low elongation at break of the polyseparates as a viscous mass. The supernatant aqueous sulfonate fi1mS layer is decanted and the residue washed two times with EXAMPLE 22 50 ccs. of water, while strongly stirring, whereupon the polymer solution is diluted with 50 ccs. of methylene 3.51 g. of 4,4-diphenyl-disulfochloride (0.01 mol), chloride. The polymer is isolated by pouring out the poly- 0.1 g. of triethylbenzyl ammonium chloride, 3.06 g. bismer solution in methanol, and drying the precipitate at (4-hydroxy-3,S-dimethylphenyl)-sulfone (0.01 mol) and 110 C. The intrinsic viscosity was measured in sym.-tetra- 15 ccs. of methylene chloride are successively brought chloroethane and found to be 0.7 dl./ g. A film cast into a three-necked 250 ccs. flask, provided with a stirfrom a methylene chloride solution shows a softening rer and a dropping funnel. While stirring at room temtemperature of ll0115 C. perature, 22.6 ccs. of sodium hydroxide solution 0.891

The polysulfonate obtained corresponds to the formula: N is dropwise added through the dropping funnel with- 21 22 in 10 minutes. After the addition of the sodium hydrox- 250 ccs. flask provided with a stirrer and a dropping ide solution, the reaction mixture is stirred at room temfunnel. While stirring at room temperature, a solution perature for another 2 hours whereby the polymer sepof 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.02 arates as a viscous mass. The supernatant aqueous layer mol) and 37.2 ccs. of sodium hydroxide solution 1.089 is decanted and the residue washed two times with 50 N is dropwise added within 10 minutes, and stirring is ccs. of water, while strongly stirring, whereupon the polycontinued for another 3 hours. Two layers are obtained mer solution is diluted with 50 cos. of methylene chlothe bottom layer of which is a viscous mass which is ride. The polymer is isolated by pouring out the polymer separated and washed with water and then diluted with solution in ethanol, and drying the precipitate at 110 methylene chloride and precipitated in ethanol. The white C. The intrinsic viscosity was measured in sym.-tetraflakes are dried at 110 C. The polymer has an intrinsic chloroethane and found to be 1.16 dl./g. A film cast viscosity in sym.-tetrachloroethane of 1.65 dL/g. whereas from a methylene chloride solution shows a softening a film cast from methylene chloride solution shows a temperature of 195 C., does not show the deficiency good elongation at break and a softening point of 160 known as crazing and is cold-drawable. 180 C. The mechanical properties measured on an The polysulfonate obtained corresponds to the formula: Instron tester are the following: tensile strength: 7.5 (i311; (3H3 I EXAMPLE 23 kg./ sq. mm, elasticity modulus: 240 kg./sq. mm., elon- 1 1f hl d (0 O1 1) 01 gation at break: 25%.

3.51 g. 'of 4,4'-dipheny-disu oc ori e mo g. of triethylbenzyl ammonium chloride, 2.56 g. of bis- EXAMPLE 26 (4-hydroxy-2,S-dimethylphenyl)-methane and ccs. of 3.51 g. of 4,4'-diphenyl-disulfochloride (0.01 mol), methylene chloride are successively brought into a three- 2.03 g. of terephthaloyl chloride (0.01 mol), 0.2 g. of necked 250 ccs. flask, provided with a stirrer and a droptriethylbenzyl ammonium chloride and 30 cos. of methylping funnel. While stirring at room temperature, 22.6 ccs. ene chloride are successively brought into a three-necked of sodium hydroxide solution 0.891 N is dropwise added 250 ccs. flask provided with a stirrer and a dropping through the dropping funnel within 10 minutes. After 30 funnel. While stirring at room temperature a solution the addition of the alkali solution, the reaction mixture is of 5 ,12 g. of 2,2-bis-(4-hydroxy-3-methylphenyl)-propane stirred at room temperature for another 90 min., where- (0.02 mol) and 39.8 ccs. of sodium hydroxide solution by the polymer separates as a viscous mass. The super- 1.017 N is dropwise added within 10 minutes, and stirnatant aqueous layer is decanted and the residue washed ring is continued for another 2 hours. After adding water two times with 100 ccs. of Water, W ile strongly t ri g, and stirirng the mixture is isolated in 2 layers the bottom whereupon the extremely viscous polymer solution is layer of which is further washed and then precipitated diluted with 100 ccs. of methylene chloride. The polymer in ethanol. The flakes are dried at 110 C. The polymer is isolated by pouring out the polymer solution in hot has an intrinsic viscosity of 0.68 dL/g. in sym.-tetrawater, and drying the precipitate at 110 C. The inchloroethane whereas afilm cast from methylene chloride trinsic viscosity was measured in sym.-tetrachloroethane solution shows good elongation at break and possesses and found to be 2.45 dl./ g. The polymer is only partially a softening point of 142-15 3 C. soluble in methylene chloride.

The polysulfonate obtained corresponds to the for- EXAMPLE 27 mula: 3.51 g. of 4,4'-diphenyl-disulfochloride (0.01 mol),

[ fi 6 1 l (5H3 (EH3 i EXAMPLE 24 0.1 g. of triethylbenzyl ammonium chloride and 20 ccs.

of 1,1,2-trichloroethane are sucessivel brought into a of 'dlphenyl'dlslilfochlonfle 9 i three-necked 250 ccs. flask provided with a stirrer and of 44'dlphenyietheridlcarboxyhc a.cld chloride a dropping funnel While stirring at room temperature (0.01 mol), 0.1 g. of triethylbenzyl ammonium chloride a Solution of g. 2 z bis (4 hydroxyphenyl) pro and 40 of methylene chloride are suqwsslvihl 55 pane (0.01 mol) in 18.6 eds. of sodium hydroxide solub-rought mm threfi'riecked 250 .flask.provlded with tion 1084 N is dropwise added within 20 minutes At the a stirrer and a dropplng funnel. While stirring at room Same time 228 g of 2 z bis (4 hydroxyphenyl) '1 Opane temperature a solution of 4.56 g. of 2,2-bis-(4-hydroxy- (O 01 m 01) 18 of sodium h droxide golufion phenyl)-propane (0.02 mol) and 37.2 ccs. of sodium y 1.084 N 10 ccs. of 1 12-trichloroethane and 0.1 g. of hydroxide solution 1.089 N is dropwise added, w1th1n 10 minutes and Stirring is continued for another 3 hours. triethylbenzyl ammonium chloride are sucesslvely brought Two layers are obtained the underlayer of which is a i a Second threq'necked flask Whlle surfing at 9 emperature a solution of 2.03 g. of terephthaloyl chloride very viscous mass WhlCh is separated and washed and (0 01 mol) in 30 ccs of 1 12 trichl0r0ethane is dm then diluted with methylene chloride and precipitated in p 0 Wise added within 20 minutes. Thereafter the contents ethanol The hght flakes are dned at 110 The poly' of the second flask is oured into the first flask and th mer has an intrinsic viscosity in sym.-tetrachloroethane p e of 1 62 d1 g A film cast from methylene chloride 801w mixture thus obtained is stirred for 3 hours. After addtion shows a good elongation and possesses a softening gi fi s Obtalged layer of int of 1 6O 18 0 C w 1c 1s was e w1 wa er an precipitate 1n ethanol. PO The flakes obtalned are dried at 100 C. The intrinsic EXAMPLE 25 viscosity of the polymer amounts to 1.35 dl./ g. in sym.-

tetrachloroethane, whereas a film cast from sym.-tetraof 4,4'41Phen31-dlS111f0Chloflde chloroethane possesses a softening point of 157162 C 2.03 g. of terephthaloylchloride (0.01 mol), 0.1 g. of

triethylbenzyl ammonium chloride and 40 ccs. of methyl- EXAMPLE 28 ene chloride are successively brought into a three-necked 7.02 g. of 4,4-diphenyl-disulfochloride (0.02 mol),

4.06 g. of isophthaloyl chloride (0.02 mol), 0.4 g. of triethylzenzyl ammonium chloride and 80 ccs. of 1,1,2- trichloroethane are successively brought into a threenecked 250 ccs. flask provided with a stirrer and a drop ping funnel. While stirring at 20 C., a solution of 9.12 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.04 mol) in 74.4 ccs. of sodium hydroxide solution 1.089 N is dropwise added within 20 minutes, and stirring is continued for another 5 hours whereupon two layers are obtained the bottom layer of which forms a viscous mass which is washed with water and then precipitated in ethanol. The tough flakes are dried at 100 C. The polymer obtained has an intrinsic viscosity of 1.14 dl./g. in sym.- tetrachloroethane whereas a film cast from methylene chloride solution shows a softening point of l42-160 C. The film obtained is flexible and shows on rough manipulation no tendency to craze.

EXAMPLE 29 4.584 g. of 2,2-bis-(4-hydroxyphenyl)-propane, 39 ccs. of sodium hydroxide solution 1.043 N, 7 ccs. of methylene chloride and 0.2 g. of triethylbenzyl ammonium chloride are brought successively into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring and cooling in ice-water, a solution of 4.806 g. of benzoylchloride-m-sulfochloride in 10 ccs. of methylene chloride is dropwise added within 10 minutes, and stirring is continued for another 2 hours whereafter two layers are obtained the bottom of which is a viscous mass which is isolated and washed with water and after dilution with methylene chloride is precipitated in methanol. The flakes are dried at 100 C. The polymer has an intrinsic viscosity of 0.80 dL/g. in sym.-tetrachloroethane, whereas a film cast from methylene chloride solution has a softening point of 122 C. The mechanical properties of the film obtained, measured on an Instron tester are the following: tensile strength: 7.5 kg./sq. mm., elasticity modulus: 280 kg./sq. mm., elongation at break: 10%.

EXAMPLE 30 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.02 mol), 38.8 ccs. of sodium hydroxide solution 1.043 N, 7 ccs. of methylene chloride and 0.2 g. of triethylbenzyl ammonium chloride are successively brought into a three necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 4.78 g. of benzoylchloride-p-sulfochioride in 10 ccs. of methylene chloride is dropwise added within 10 minutes, whereupon stirring is continued for 2 hours. Two layers are obtained the bottom layer of which is a viscous mass which is washed with water and precipitated in methanol. The flakes are dried at 100 C. The polymer has an intrinsic viscosity of 0.80 dL/g. in syrn.-tetrachloroethane, whereas a film cast from methylene chloride solution shows a softening point of 155 C., and an elongation at break of 10%.

EXAMPLE 3 l 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.02 mol), 45.3 ccs. of sodium hydroxide solution 0.891 N, 0.2 g. of triethylbenzyl ammonium chloride and 10 ccs. of methylene chloride are successively brought into a threenecked 250 ccs. flask, provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 2.03 g. of terephthaloyl chloride (0.01 mol) and 1.55 g. of benzoylchloride-m-sulfochloride in 10 ccs. of methylene chloride is dropwise added through the dropping funnel within minutes. After the addition of the diacid chloride solution, the reaction mixture is stirred at room temperature for another 75 min., whereby the polymer separates as a viscous mass. The supernatant aqueous layer is decanted and the residue washed two times with 50 ccs. of water, while strongly stirring, whereupon the polymer solution is diluted with 50 ccs. of methylene chloride. The polymer is isolated by pouring out the polymer solution in methanol, and drying the precipitate at 110 C. The intrinsic viscosity was meausred in symtetrachloroethane and found to be 0.7 dl./ g. A film cast from a methylene chloride solution shows a softening temperature of 150 C. and is cold-drawable. The elongation at break is 45%.

EXAMPLE 32 9.12 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.04 mol), 77.6 ccs. of sodium hydroxide solution 1.043 N, 0.4 g. of triethylbenzyl ammonium chloride and 10 ccs. of methylene chloride are successively brought into a threenecked 250 ccs. flask provided'with a stirrer and a dropping funnel. While stirring at room temperature a solution of 5.5 g. of 1,3-benzene-disulfochloride (0.02) mol and 4.06 g. of isophthaloylchloride (0.02 mol) in 20 ccs. of methylene chloride is dropwise added within 5 minutes, and stirring is continued for another 1 hour. Two layers are obtained the bottom layer of which is washed with water and precipitated in methanol. The flakes obtained are dried at 110 C. The polymer has an intrinsic viscosity of 0.05 dl./ g. in sym-tetrachloroethane and a film cast from methylene chloride solution shows a softening point of 110 C.

EXAMPLE 33 9.12 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.04 mol), 81.5 ccs. of sodium hydroxide solution 0.9905 N, 0.4 g. triethylbenzyl ammonium chloride and 20 ccs. of methylene chloride are successively brought into a threenecked 250 ccs. flask, provided with a stirrer and a dropping funnel. While stirring at room temperature, a solution of 4.06 g. of isophthaloyl chloride (0.02 mol) and 3.1 ccs. of benzoylchloride-m-sulfochloride (0.02 mol) into 20 ccs. of methylene chloride is dropwise added through the dropping funnel within 20 minutes. After the addition of the diacid chloride solution, the reaction mixture is stirred at room temperature for another 2 hours whereby the polymer separates as a viscous mass. The supernatant aqueous layer is decanted and the residue washed two times with 50 ccs. of water, while strongly stirring, whereupon the polymer solution is diluted with 50 ccs. of methylene chloride. The polymer is isolated by pouring out the polymer solution in hot water, and drying the precipitate at C. The intrinsic viscosity was measured in sym-tetrachloroethane and found to be 0.74 dl./ g.

. A film cast from a methylene chloride solution shows a softening temperature at C., a tensile strength of 8 kg./ sq. mm., a yield strength of 7.1 kg./sq. mm., an elasticity modulus of 225 kg./sq. mm. and an elongation at break of 15%.

EXAMPLE 34 5.616 g. of 4,4'-diphenyl-disulfochloride (0.016 mol), 0.2 g. of triethylbenzyl ammonium chloride, 15 ccs. of methylene chloride, 4.104 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.018 mol) and 39.3 ccs. of sodium hydroxide solution 0.963 N are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 0.740 g. of 2,2-bis-(4-hydroxyphenyl)-propane-bis-chloroformate (0.0021 mol) in 15 ccs. of methylene chloride is dropwise added within 10 minutes and stirring is continued for another 1 /2 hours whereafter two layers are obtained the bottom layer of which, a viscous mass, is washed with water, diluted with methylene chloride and precipitated in boiling water. The rough flakes are dried at 110 C. The polymer has an intrinsic viscosity of 2.18 dl./ g. in sym-tetrachloroethane whereas a film cast from methylene chloride solution shows a softening point of -147l50 C. The film is flexible and possesses a good elongation at break: 10%.

EXAMPLE '35 3.51 g. of 4,4'-diphenyl-disulfochloride (0.01 mol), 0.2 g. of triethylbenzyl ammonium chloride, 15 ccs. of methylene chloride, 3.42 g. of 2,2-bis-(4-hydroxyphenyl)-pro- 25 pane (0.015 mol) and 32.8 ccs. of sodium hydroxide solution 0.963 N are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 1.8 g. of 2,2-bis-(4-hydroxyphenyl)-propane-bis-chloroformate (0.0051 mol) in cos. of methylene chloride is added to this mixture within 7 minutes, whereupon stirring is continued for another 1 hour. Two layers are obtained the bottom layer of which is very viscous. This layer is washed with water, diluted with methylene chloride and poured out in boiling water. Rough flakes are obtained which are dried at 110 C. The polymer has an intrinsic viscosity of 2.2 dl./ g. in sym-tetrachloroethane, whereas the film cast from methylene chloride solution shows a softening point of 148 C. The film is flexible and shows on rough manipulation no tendency to craze.

'EXAMPLE 36 1.755 g. of 4,4'-diphenyl-disulfochloride (0.005 mol), 0.2 g. of triethylbenzyl ammonium chloride, 10 ccs. of methylene chloride, 3.42 g. of 2,2-bis-(4 hydroxyphenyl)- propane (0.015 mol) and 32.8 ccs. of sodium hydroxide solution 0.963 N are successively brought into a threenecked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 3.88 g. of 2,2-bis-(4-hydroxyphenyl)-propane-bischloroformate (0.11 mol) in ccs. of methylene chloride is dropwise added within 10 minutes and stirring is continued for another 1 hour whereupon two layers are obtained the bottom layer of which isa viscous mass which is washed with water, diluted with methylene chloride and precipitated in boiling water. The polymer is dried at 100 C. and has an intrinsic viscosity of 1.32 dl./ g. in sym-tetrachloroethane, whereas a film cast from methylene chloride solution has a softening point of 140 C.

EXAMPLE 37 4.11 g. of 4,4-diphenyl-disulfochloride, 0.3 g. of triethylbenzyl ammonium chloride, 15 ccs. of methylene chloride, 5.34 g. of 2,2-bis-(4-hydroxyphenyl)-propane and 49.2 cos. of sodium hydroxide solution 0.963 N are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring and cooling in ice-water, a solution of 2.813 g. of sebacoyl chloride in 15 ccs. of methylene chloride is dropwise added within 15 minutes and stirring is continued for another 1 hour. The bottom layer is washed with water and precipitated in hot water. The polymer is dried at 110 C. and has an intrinsic viscosity of 0.51 dl./g. in sym-tetrachloroethane, and a film cast from methylene chloride solution has a softening point of 130 C.

EXAMPLE as 3.51 g. of 4,4'-diphenyldisulfochloride (0.01 mol), 3.53 g. of 2,2-bis-(4-hydroxyphenyl)propane-bis-chloroformate (0.01 mol), 0.2 g. of triethylbenzyl ammonium chloride and 30 ccs. of methylene chloride are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring, a solution of 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.02 mol) in 42 cos. of sodium hydroxide solution 0.963 N is dropwise added within 10 minutes to this mixture, and stirring is continued for another 1 hour, whereupon the bottom layer is separated, washed with water and precipitated in boiling water. The polymer is dried at 110 C. and has an intrinsic viscosity of 1.18 dl./g. in sym-tetrachloroethane, and a film cast from a methylene chloride solution shows a softening point of 147 C.

EXAMPLE 39' 70.2 g. of 4,4-diphenyl-disulfochloride (0.2 mol), 35.3 g. of 2,2-bis-(4-hydroxyphenyl)-propane-bis-chloroformate (0.1 mol), 3 g. of triethylbenzyl ammonium chloride and 500 ccs. of methylene chloride are successively brought into a three-necked 3 liter flask provided with a stirrer, a dropping funnel and a thermometer. While stirring at a temperature of 25 C. a solution of 68.4 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.3 mol), 25 g. of sodium hydroxide and 600 ccs. of water is dropwise added within 20 minutes, and stirring is continued for another 1 hour. Two layers are obtained the bottom layer of which is a viscous mass which is washed with water and then after dilution with 500 ccs. of methylene chloride poured out into boiling water. The tough flakes are dried at 110 C. The polymer obtained has an intrinsic viscosity of 1.60 dl./ g. in sym-tetrachloroethane, and a film cast from methylene chloride solution shows a softening point of 150 C.

EXAMPLE 40 28.80 g. of 4,4'-diphenyl-disulfochloride (0.08 mol), 3.73 g. of 2,2-bis-(4-hydroxyphenyl)-propane-bis-chloro formate (0.01056 mol), 1 g. of triethylbenzyl ammonium chloride and 150 ccs. of methylene chloride are successively placed in a three-necked 1 liter flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 20.52 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.09 mol) and 7.3 g. of sodium hydroxide in 150 ccs. of water is dropwise added within 7 minutes, and stirring is continued for 1% hours. Two layers are obtained, the bottom layer of which is a viscous mass which is washed with water, diluted with ccs. of methylene chloride and then precipitated in boiling water. The "white flakes are dried at 100 C. The polymer has an intrinsic viscosity of 1 dl./g. in sym-tetrachloroethane, and a film cast from a methylene chloride solution shows a softening point of 154 C.

EXAMPLE 41 7.02 g. of 4,4-diphenyl-disulfochloride (0.02 mol), 0.2 g. of triethylbenzyl ammonium chloride and 30 ccs. of methylene chloride are successively placed in a threenecked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.02 mol) in 42 ccs. of sodium hydroxide solution 0.963 N is dropwise added within 10 minutes and stirring is continued for another 5 to 10 minutes. As soon as a thick milky mass is obtained, a solution of 3.60 g. of 2,2 bis (4 hydroxyphenyl) propane bis chloroformate (0.0102 mol), 0.1 g. of triethylbenzyl ammonium chloride and 20 ccs. of methylene chloride is added thereto. Whilst stirring a solution of 2.28 g. of 2,2-bis-(4- hydroxyphenyl)-propane (0.01 mol) in 22 ccs. of sodium hydroxide solution 0.963 N is added within 5 minutes. The mixture is further stirred for 1% hour whereupon two layers are obtained the bottom layer of which is a viscous layer which is washed with water, diluted with methylene chloride and poured out into boiling Water. The white flakes are dried at C. and the polymer obtained has an intrinsic viscosity of 1.03 dl./g. in symtetrachloroethane, and a film cast from methylene chloride solution shows a softening point of 158 C EXAMPLE 42 7.02 g. of 4,4'-diphenyl-disulfochloride (0.02 mol), 0.2 g. of triethylbenzyl ammonium chloride and 25 ccs. of methylene chloride are successively brought into a threenecked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane 0.02 mol) in 42 cos. of sodium hydroxide solution 0.963 N is dropwise added within 10 minutes. At the same time a solution of 3.60 g. of 2,2-bis-(4-hydroxyphenylpropane -bis-ch1oroformate (0.0102 mol), 0.1 g. of triethylbenzyl ammonium chloride and 25 ccs. of methylene chloride is brought into a second 250 ccs. flask. Hereto is dropwise added within 10 minutes, and while stirring a solution of 2.28 g. of 2,2-bis-(4-hydroxypheny1)-propane (0.01 mol) in 22 ccs. of sodium hydroxide solution 0.963 N. Both mixtures are now separately stirred for minutes. Thereafter the second flask content is added to the first and the whole is further stirred for 1% hour whereupon the supernatant water layer is decanted and the polymer residue washed with water and poured out into boiling water. The flakes are dried as 110 C. and the polymer obtained has an intrinsic viscosity of 1.10 dl./ g. in symtetrachloroethane, and a film cast from a methylene chloride solution shows a softening point of 157 C.

EXAMPLE 43 5.616 g. of 4,4'-diphenyldisulfochloride (0.016 mol), 0.2 g. of triethylbenzyl ammonium chloride and 20 cos. of methylene chloride are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution consisting of 4.104 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.018 mol) in 38.2 ccs. of sodium hydroxide solution 0.963 N is dropwise added within 15 minutes. After further stirring for 5 minutes, a milky sticky mass is obtained whereupon a solution of 0.740 g. of 2,2-bis-(4-hydroxyphenyl)-propane -bis-chloroformate (0.0021 mol) in ccs. of methylene dichloride is added. Next the residual first sodium hydroxide solution is also rapidly added while the reaction mixture is further stirred for another one hour. The two layers obtained are separated and the bottom layer is washed with water, diluted with methylene chloride and poured out into boiling water. The soft flakes are dried at 110 C., and the polymer obtained has an intrinsic viscosity of 1.17 d1./ g. in sym-tetrachloroethane, and a film cast from a methyl ene chloride solution shows a softening point of 155 C.

EXAMPLE 44 5.37 g. of 4,4-diphenyl-disulfochloride (0.0153 mol), 0.3 g. of triethylbenzyl ammonium chloride, ccs. of methylene chloride, 6.977 g. of 2,2-bis-(4-hydroxy-phenyl)-propane (0.0306 mol) and 66 ccs. oii sodium hydroxide solution 0.963 N are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 2.92 g. of ethylene glycol-bischloroformate (0.0156 mol) in 10 ccs. of methylene chloride is dropwise added within 15 minutes, and stirring is continued for another /2 hour. The bottom layer is separated, washed with water and poured out into boiling Water. The flakes are dried at 110 C. and the polymer obtained has an intrinsic viscosity of 0.74 dl./ g. in sym-tetrachloroethane, and a film cast from methylene chloride solution shows a softening point of 115 C.

EXAMPLE 45 3.67 g. of 4,4-diphenylether-disulfochloride (0.01 mol), 3.50 g. of 2,2-bis-(4-hydroxyphenyl)-propane -bischloroformate (0.0102 mol), 0.2 g. of triethylbenzyl am monium chloride and ccs. of methylene chloride are successively brought into a three-necked 250 ccs. flask provided with a stirrer and a dropping funnel. While stirring and at room temperature a solution of 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.2 mol) in 41.5 ccs. of sodium hydroxide solution 0.963 N is dropwise added within 15 minutes, and stirring is continued for another 45 minutes. The two layers obtained are separated and the bottom layer is washed with water and then poured out into boiling water. The flakes are dried at 110 C. The polymer has an intrinsic viscosity of 0.87 dl./g. in sy-m-tetrachloroethane and a film cast from a methylene chloride solution shows a softening point of 110 C.

EXAMPLE 46 2.75 g. of 1,3-benzene-disulfochloride (0.01 mol), 3.53 g. of 2,2 bis-(4-hydroxyphenyl)-propane-bis-chloroformate (0.01 mol), 0.2 g. of triethylbenzyl ammonium chloride and 25 ccs. of methylene chloride are successively brought into a three-necked 250 ccs. flask provided with a stirrer, and a dropping funnel. While stirring, a solution of 4.56 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.02 mol) and 41.5 ccs. of sodium hydroxide solution 0.963 N is dropwise added within 10 minutes. Stirring is continued for another 40 minutes, the bottom layer is separated, Washed with water and poured out into boiling water. The flakes are dried at 110 C. and the polymer obtained has an intrinsic viscosity of 0.66 dL/g. in symtetrachloroethane, and a film cast from a methylene chloride solution shows a softening point of C.

EXAMPLE 47 4.56 g. of 2,2-bis-(4-hydroxyphenyl)propane (0.02 mol), 41.5 ccs. of sodium hydroxide solution 0.963 N, 10 ccs. of methylene chloride and 0.2 g. of triethylbenzyl ammonium chloride are successively added to a threenecked 250 ccs. flask, provided with a stirrer and a dropping funnel. While stirring at room temperature a solution of 3.65 g. of 4,4-diphenylmethane-disulfochloride (0.01 mol), 3.57 g. of 2,2-bis-(4-hydroxypheny1)propanebis-chloroformate (0.0101 mol) and 15 cos. of methylene chloride is dropwise added within 10 minutes. Stirring is continued for /2 hour whereafter the bottom layer is separated from the mixture, washed with water and then poured out into boiling water. The flakes are dried at C. The polymer obtained has an intrinsic viscosity of 0.76 dl./g. in syrn-tetrachloroethane and a film cast from a methylene chloride solution shows a softening point of C.

EXAMPLE 48 27.50 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.12 mol), ccs. of water, 13.70 g. of sodium hydroxide and 50 ccs. of methylene chloride are successively brought into a three-necked 1 l. flask, provided with a thermometer, a gas inlet and a stirrer, and while stirring 14.13 g. of prosgene is added within 1% hours at 2025 C. Next, 42.12 g. of 4,4-diphenyldisulfochloride (0.12 mol), 2.5 g. of triethylbenzylammoniurn chloride and 175 ccs. of methylene chloride are added. While further stirring, a solution of 27.50 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.12 mol) and 9.8 g. of sodium hydroxide in 200 ccs. of water is dropwise added within 10 minutes, and stirring is continued for another 1% hours 200 cos. of water are added to the mixture and stirring is continued for A h. The bottom layer is separated, washed with water and poured out into boiling water. The flakes are dried at 110 C. The polymer has an intrinsic viscosity of 0.4 dL/g. in sym.-tetrachloroethane.

EXAMPLE 49 3.51 g. of 4,4'-diphenyl-disulfochloride (0.01 mol), 3.56 g. of [2,2-bis-(4-hydroxyphenyl) propanej-bischloroformate (0.0101 mol), 0.2 g. of triethylbenzylammonium chloride, 5.12 g. of bis-(4-hydroxy-3,5-dimethylphenyl)-diphenylmethane and 25 ccs. of methylene chloride are successively brought into a three-necked 25 O ccs. flask provided with a stirrer and a dropping funnel. While stirring at room temperature 41.5 ccs. of sodium hydroxide solution 0.963 N is dropwise added within 10 minutes, and stirring is continued for /2 hour. The two layers are separated whereupon the bottom layer is washed with Water and poured out into boiling water. The flakes are dried at 110 C. The polymer obtained has an intrinsic viscosity of 0.42 dl./ g. in sym.-tetrachloroethane.

EXAMPLE 5 0 27.50 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.12 mol), 11.70 g. of sodium hydroxide, ccs. of water, 100 ccs. of methylene chloride and 1.2 g. of triethylbenzylammonium chloride are succesively brought into a fournecked 0.5 l. flask, provided with a stirrer, a gas inlet and a thermometer. While stirring at 2025 C., 7.15 g. of phosgene and 21.06 g. of 4,4'-diphenyldisulfochloride 29 (0.06 mol) are dropwise added within 30 minutes to this mixture, and stirring is continued for 1% hours. Two layers are obtained the bottom layer of which is viscous and is separated and washed with water. After dilution with 100 ccs. of methylene chloride the product is poured out into boiling water. The flakes are dried at 110 C. The polymer obtained has an intrinsic viscosity of 0.72 dl./g. and a film cast from methylene chloride solution shows a good elongation at break and a softening point of 145 C.

EXAMPLE 51 7.02 g. of 4,4-diphenyl-disulfochloride (0.02 mol), 2.9 ccs. of phthaloylchloride (0.02 mol), 0.4 g. of triethylbenzoyl ammonium chloride and 40 ccs. of methylene chloride are successively brought into a three-necked 250 ccs. flask, provided with a stirrer and a dropping funnel. While stirring at C., a solution of 9.12 g. of 2,2-bis- (4-hydroxypl1enyl)-propane (0.04 mol) into 84 ccs. of sodium hydroxide solution 0.963 N is dropwise added through the dropping funnel within 10 minutes. After the addition of the bisphenate solution, the reaction mixture is stirred at room temperature for another 2 hours whereby the polymer separates as a viscous mass. The supernatant water is decanted and the residue washed two times with 50 ccs. of water, whilst strongly stirring, whereupon the polymer layer is diluted with 50 ccs. of methylene chloride. The product is obtained by pouring out the polymer solution in methanol, and drying the precipitate at 100 C. The intrinsic viscosity was measured in sym.- tetrachloroethane and found to be 0.70 dl./ g. A film cast from a methylene chloride solution shows a softening temperature of 145 C.

EXAMPLE 52 7.02 g. of 4,4-diphenyl-disulfochloride (0.02 mol), 0.2 g. of triethylbenzyl ammonium chloride, 1.6 g. of pentadecyl-resorcinol (0.005 mol) and 25 ccs. of methylene chloride are successively brought into a threenecked 250 ccs. flask, provided with a stirrer and a dropping funnel. While stirring at room temperature, a solution of 3.42 g. of 2,2-bis-(4-hydroxyphenyl)-propane (0.015 mol) and 41 ccs. of sodium hydroxide solution 0.9905 N is dropwise added through the dropping funnel within minutes. After the addition of the diphenol solution, the reaction mixture is stirred at room temperature for another 60 minutes, whereby the polymer separates as a viscous mass. The supernatant aqueous layer is decanted and the residue washed two times with 50 ccs. of water, while strongly stirring, whereupon the polymer solution is diluted with 50 ccs. of methylene chloride. The polymer is isolated by pouring out the polymer solution in ethanol, and drying the precipitate at 110 C. The intrinsic viscosity was measured in sym-tetrachloroethane and found to be 1.45 dl./ g.

EXAMPLE 53 To a three-necked 250 ccs. flask provided with stirrer and dropping funnel are charged 4.56 g. (0.02 mol) of 2,2-bis-(4-hydroxyphenyl) propane, 40 ccs. of sodium hydroxide l N (0.04 mol), 200 mg. of triethylbenzyl ammonium chloride and 10 ccs. of methylene chloride, and within 5 minutes a solution of 3.05 ccs. of benzoylchloride-m-sulfochloride is added in 10 ccs. of methylene chloride. After rinsing the funnel with 5 ccs. of methylene chloride stirring is continued for another 1 hour. During the polycondensation the reaction mixture separates into two layers, and the supernatant water is decanted from the very viscous organic layer obtained. After washing the organic layer with water the polymer is precipitated by pouring out into boiling water. The flakes obtained are then dried at 110 C. Yield: 7.5 g. The intrinsic viscosity determined in tetrachloroethane amounts to 0.9 dl./ g.

The polymer obtained has the following formula:

r e L CH (1) R R R R g I HO OH where n is an integer from 0 to 1, each R is selected from the group consisting of hydrogen, alkyl and halogen and X is selected from the group consisting of i" u 1 C -o -o- -0- s and s C J I l Y representing the atoms necessary to close a cycloaliphatic ring and R and R" each representing a member of the group consisting of hydrogen, alkyl haloalkyl, a phenyl radical, and a cycloalkyl radical, alkyl in all instances being lower alkyl and haloand halogen in all instances being a halogen atom of atomic weight less than and (2) HOArOH where Ar is a member of the group consisting of a phenyl radical and a naphthalene radical; said polyester having an intrinsic viscosity of at least about 0.5 dl./ g. when measured in a solution in tetrachloroethane at 25 C. and capable of forming a self-supporting film.

2. Polyester of claim 1 wherein said polybasic acid is benzene disulfonic acid, n is 1, X is a member of the group consisting of dimethylmethylene and sulfonyl and each R is a member of the group consisting of hydrogen and chlorine.

3. The polyester of claim 1 wherein said polybasic acid is diphenyl ether disulfonic acid, n is 1, X is a member of the group consisting of dimethylmethylene and sulfonyl, and each R is hydrogen.

4. The polyester of claim 1 wherein said polybasic acid is diphenyl disulfonic acid and said bisphenolic compound is 2,2-bis(4-hydroxyphenyl)propane.

References Cited UNITED STATES PATENTS 2,035,578 3/1936 Wagner 26047 2,708,617 5/1955 Magat et al. 26047 3,028,364 4/ 1962 Conix et a1. 260-47 3,030,331 4/1962 Goldberg 260'-47 HAROLD D. ANDERSON, Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 1 289 Dated April 1970 Inventor(s) Andre Jan CONIX et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Priority Paragraph to read:

- Claims priority, Belgium SN 37,910 filed March 7, 1958; Belgium SN 39,450 filed December 22, 1959; and Great Britian SN 543/1960 filed January 6, 1960.

Signed and sealed this 18th day of April 1972.

(SEAL) Attest:

EDWARD M.FLETCHEH,JR. ROBERT GOTTSCHALK Abtesting Officer Commissioner of Patents 

1. A HIGH MOLECULAR WEIGHT LINEAR POLYESTER OF POLYBASIC ACID AND POLYHYDRIC ALCOHOL, SAID POLYBASIC ACID CONSISTING ESSENTIALLY OF AT LEAST ONE ACID SELECTED FROM THE GROUP CONSISTING OF AROMATIC DISULFONIC ACIDS AND AROMATIC MONOCARBOXYSULFONIC ACIDS, AND SAID POLYHYDRIC ALCOHOL CONSISTING ESSENTIALLY OF AT LEAST ONE BISPHENOLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE FOLLOWING FORMULAE: 